Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/063—Titanium; Oxides or hydroxides thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/18—Arsenic, antimony or bismuth
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
  • B01J37/033—Using Hydrolysis
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/48—Separation; Purification; Stabilisation; Use of additives
  • C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
  • C11C3/10—Ester interchange
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0209—Impregnation involving a reaction between the support and a fluid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

• the present invention relates to a new process for the manufacture of esters of monocarboxylic acids from vegetable or animal oils.
• the reaction which is aimed primarily is a transesterification carried out according to Scheme I below and optionally a combined esterification and transesterification reaction, the esterification being carried out according to Scheme II below.
• the fatty acid chains are represented by oleic type chains.
• Fatty esters are currently used in many applications as diesel fuels, domestic fuels, solvents, basic compounds for manufacture of sulfonates of fatty alcohols, amides, ester dimers, etc.
• catalysts commonly used are simple alkaline derivatives, such as sodium alcoholates, sodium hydroxide or potassium hydroxide, under fairly soft (temperature of 50 to 80 ° C and atmospheric pressure), as can be read in many patents or publications, for example in JAOCS 61 , 343-348 (1984), however, a product can not be produced. pure usable as a fuel and glycerin standards that after many steps.
• alkaline catalysts we find, also in the glycerine than in the ester, these alkaline compounds, which must be removed by washing and / or by neutralization in the ester fraction and then drying it. In the glycerin phase, it is necessary to neutralize the soaps and the alcoholates present, sometimes to eliminate the formed salts.
• the glycerin thus obtained contains water generally between 5% and 40% by weight. mass. It also contains the salts resulting from the neutralization of the alkaline catalyst, by example of sodium chloride when the catalyst is soda or methylate of sodium and when the neutralization is carried out with hydrochloric acid.
• the salt concentration in glycerin resulting from these processes is generally understood between 3% and 6% by weight. Obtaining high purity glycerol from glycerine resulting from these processes therefore imposes purification steps such as distillation under reduced pressure that can sometimes be associated with treatments on exchange resins.
• the transesterification catalyst which converts oil and methanol into a methyl ester, is an alumina or a mixture of alumina and alumina. ferrous oxide.
• US Pat. No. 5,908,946 describes a method that can work. continuously or batchwise and using solid and insoluble catalysts.
• the catalysts used are either zinc oxide or a mixture of zinc oxide and of alumina, a zinc aluminate.
• All the catalysts under consideration are in the form of powder, beads, extrudates or pellets.
• the use of alumina has two favorable effects.
• the first is to increase its specific surface area titanium in its main crystalline forms (anatase or rutile) and zirconia under its main crystalline forms (quadratic, monoclinic and cubic) are known to have small specific surfaces.
• the second is to create a much more stable compound, especially vis-à-vis conditions under which the titanium, zirconium or antimony tend to form titanium, zirconium or antimony soaps.
• catalysts based on titanium, zirconium or antimony are their ability to catalyze the transesterification of the oil with alcohols heavier than the methanol.
• solid catalysts catalyze the reactions of transesterification and esterification according to a heterogeneous catalysis process, ie that the solid catalyst used on the one hand is not consumed in the reaction and on the other part is never dissolved in the reaction medium but remains in the solid form and will be therefore separated from the liquid reaction medium without loss of catalyst and without pollution of the reaction medium by the presence of catalyst or catalyst residue.
• This kind of catalyst is compatible with use in a continuous industrial process by example in fixed bed in which the catalyst charge can be used during a very long life without loss of activity.
• the ester and glycerol obtained do not contain impurities from the catalyst. Therefore, no purification treatment will be applied to remove the catalyst or residues thereof, unlike processes using working catalysts according to a homogeneous process where the catalyst or its residues are, after reaction, localized in the same phase as the ester and / or that glycerin.
• the final purification is reduced to a minimum, while by allowing to obtain an ester which is to the specifications fuel, and a glycerin of purity between 95% and 99.9% and preferably between 98% and 99.9%.
• cooking oils various animal oils, such as fish oils, tallow, lard, rendering and even fats.
• oils used it is still possible to indicate oils partially modified for example by polymerization or oligomerization, such as, for example, "standolies" of linseed oils, sunflower and blown vegetable oils.
• the nature of the alcohol involved in the process of the invention plays a role important in the activity of transesterification.
• various aliphatic monoalcohols containing, for example, from 1 to 18 carbon atoms carbon, preferably from 1 to 12 carbon atoms.
• the most active is methyl alcohol.
• ethyl alcohol and isopropyl, propyl and butyl alcohols isobutyl and even amyl can be engaged.
• We can also use heavier alcohols such as ethyl hexyl alcohol or lauric alcohol.
• the ethyl ester it is possible to use from 1 to 50%, preferably from 1 to 10% of methyl alcohol so as to increase the conversion.
• US-A-5 169 822 teaches deposition in a non-aqueous medium of titanium alkoxides on inorganic carriers (among others).
• the article by S. Kumar et al. in Mat. Lett. 43 (2000) 286 teaches the precipitation of a boehmite sol with a titanium dioxide sol.
• the titanium sol is prepared by stabilization with acetic acid.
• a preferred method is the precipitation of ZrO (NO 3 ) 2 by hydrazine, with or without Al (NO 3 ) 3 (e.g., the method cited by Ciuparu et al., J. Mater Sci. 19 (2000) 931).
• the sources of zirconium may be gels resulting from the hydrolysis of the preceding sources, thus obtaining a form of partially hydrated zirconium oxide of chemical formula (ZrO 2 , zH 2 O) with z between 0 and 5. It It is also advantageous to use dehydrated zirconium oxide, amorphous or crystallized, which in the latter case has quadratic, monoclinic or cubic crystallographic structures known to those skilled in the art.
• the sources of antimony can be gels resulting from the hydrolysis of the preceding sources, thus obtaining a form of partially hydrated antimony oxide of chemical formula (SbO y , zH 2 O) with between 1.2 and 2,6 and z between 0 and 5. It is also advantageous to use oxides of antimony (Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 ) more or less dehydrated, amorphous or crystallized, which has in this case crystallographic structures known to those skilled in the art.
• the inorganic aluminum salts can also be advantageously used, namely chlorides, nitrates, sulphates, etc.
• the aluminum source may be basic, in which case the aluminum is in aluminate form (AlO 2 - ).
• the counterion may be an alkaline (Li, Na, K, Cs) and more generally any positive counterion (NH 4 + for example).
• any alumina compound of the general formula Al 2 O 3 , nH 2 O may be used. Its specific surface is between 100 and 600 m 2 / g.
• hydrated alumina compounds such as: hydrargillite, gibbsite, bayerite, boehmite, pseudo-boehmite and amorphous or essentially amorphous aluminas are useful. It is also possible to use the dehydrated forms of these compounds which consist of transition aluminas and which comprise at least one phase taken from the group: rho, khi, eta, kappa, theta, delta, gamma and alpha, which differentiate essentially on the organization of their crystalline structure.
• titanium oxide, zirconium oxide or antimony oxide preferably 23% of titanium, zirconium or antimony and even more preferably 50% of titanium, zirconium or antimony.
• the oxides of titanium, zirconium or antimony shall be in predominantly amorphous or micro-crystalline form, remarkable in this by the absence on the ray diffraction diagram X crystalline forms, known to those skilled in the art, of titanium oxide, zirconium or antimony.
• the catalyst will generally have a specific surface area of between 10 and 500 m 2 / g, preferably between 50 and 400 m 2 / g and more preferably between 80 and 300 m 2 / g.
• the pore volume will be between 0.1 cm 3 / g and 1.2 cm 3 / g, and preferably greater than 0.2 cm 3 / g.
• the porous distribution will be between 0.001 microns and 0.1 microns.
• the transesterification is carried out in the absence of catalyst, or in an autoclave, either in a fixed bed with inert supports, such as silicon carbide, it is possible to obtain certain temperatures generally greater than or equal to 250 ° C, conversions exceed 80%, but at very low VVH and with very long residence times.
• the thermal reaction therefore exists and it is sometimes difficult to decide between the catalytic effect and the thermal effect, which explains why with simple aluminas it is possible to obtain high conversions.
• the object of the process of the invention is to obtain these Conversions with reasonable residence times, so reasonable VVH.
• the operating conditions used depend clearly on the method chosen. If a batch reaction is used, we can work in one or two stages, that is to say perform a first reaction up to 85% to 95% conversion, cool in evaporating the excess methanol, decant the glycerine and finish the reaction by warming to new and adding alcohol to achieve total conversion. We can also aim a 98% conversion by working long enough in one step.
• the introduction of the alcohol can be advantageously fractionated.
• the introduction to two levels in the tubular reactor can be operated as follows: reactor with the oil and about 2/3 of the alcohol to put into play, then introduction of Alcohol complement approximately at the top third of the catalytic bed.
• ester of the same color as the starting oil and a colorless glycerin after decantation.
• the ester can be passed on resin, earth and / or activated carbon, as well as glycerine.
• the compounds produced are analyzed either by gas chromatography for esters and glycerin, or, more rapidly, by liquid chromatography exclusion for esters. It can be seen that the process of the invention, unlike known processes carried out in homogeneous basic catalysis with monoalcohols, does not no, or very little, of sterol esters. Sterol esters, which are heavy products, can cause deposits in the injectors.
• Catalyst 1.2 is prepared according to S. Kumar et al., Mat. Lett. 43 (2000) 286. 336 g of titanium isopropoxide are introduced into a reactor. 600 ml of acetic acid are added to the titanium solution and the whole is mixed for 30 minutes. To this solution, 1800 ml of water are slowly added while maintaining constant stirring. To this solution, 708 g of boehmite sol at 10% by weight is added. Stirring is maintained for 30 minutes. The mixture is placed under autogenous pressure at 100 ° C to obtain gelation. The gel obtained is filtered, dried and then atomized. The powder obtained is shaped by extrusion. The extrudates are then calcined at 600 ° C. for 3 hours.
• X-ray diffraction analysis shows the presence of crystalline phase, characteristic of the presence of gamma-alumina. No characteristic rutile or anatase phase is detected.
• the specific surface area measured by the BET method is 145 m 2 / g.
• the content of alumina and titanium dioxide measured by X-ray fluorescence is respectively 51 and 49% by weight.
• Catalyst 1.3 is prepared by impregnation of titanium butoxide on Catalyst 1.1.
• the alumina is calcined at 400 ° C. for 1 hour.
• 55.45 g of titanium butoxide is mixed with 5 ml of heptane and then poured slowly over 87 g of alumina. The whole is stirred for 24 hours.
• the solid obtained is placed in ambient air for 72 h and then dried in an oven.
• the catalyst is calcined at 500 ° C for 4 hours.
• X-ray diffraction analysis shows the presence of crystalline phase, characteristic of the presence of gamma-alumina. No characteristic rutile or anatase phase is detected.
• the specific surface area measured by the BET method is 185 m 2 / g.
• the content of alumina and titanium dioxide measured by X-ray fluorescence is respectively 87.5 and 12.5% by weight.
• Catalyst 1.4 is prepared according to the teaching of US Pat. No. 4,490,479. 91 g of boehmite (Pural SB3) are mixed with 39 g of titanium gel (Gel G5 Millenium) in the presence of 3.2 g of 70% nitric acid and 122 g of water. The components are kneaded for 1 hour to form a paste. The pulp thus obtained is converted into extrudates of 1.6 mm in diameter which are dried at 120 ° C for 20 h and calcined in air at 450 ° C for 10 h. X-ray diffraction analysis shows the presence of a crystalline phase, characteristic of the presence of gamma-alumina.
• the specific surface area measured by the BET method is 163 m 2 / g.
• the content of alumina and titanium dioxide measured by X-ray fluorescence is 70.5 and 29.5% by weight, respectively.
• a titanium support SCS41 is used. Its specific surface is 98 m 2 / g.
• Catalyst 1.6 is prepared according to the teaching of US Pat. No. 4,490,479.
• 95 g of boehmite (Pural SB3) are mixed with 30 g of titanium dioxide in the presence of 7 g of 70% nitric acid and g of water.
• the components are mixed for 1 hour to form a paste.
• the pulp thus obtained is converted into 1.4 mm diameter extrudates which are dried at 120 ° C. for 20 hours and calcined in air at 550 ° C. for 10 hours.
• X-ray diffraction analysis shows the presence of crystalline phases, characteristic of the presence of gamma-alumina and anatase.
• the specific surface area measured by the BET method is 136 m 2 / g.
• the content of alumina and titanium dioxide measured by X-ray fluorescence is 69.2 and 31.8% by weight, respectively.
• Catalyst 2.2 is prepared according to reference Ciuparu (J. Mater Sci Lett 19 (2000) 931) .Zirconyl nitrate is mixed with hydrazine and refluxed for 120 hours. The gel obtained is filtered, dried and then atomized. The powder obtained is shaped by extrusion. The extrudates are then calcined at 550 ° C. for 4 hours. X-ray diffraction analysis results in amorphous zirconia, no streak characteristic of known crystallographic phases of zirconia being detected. The specific surface area measured by the BET method is 250 m 2 / g. The zirconia content is 100%.
• Catalyst 2.3 is prepared by impregnating zirconium n-butoxide on Catalyst 1.1.
• the alumina is calcined at 400 ° C. for 1 hour.
• 92.7 g of zirconium n-butoxide is mixed with 64 ml of heptane and then poured slowly over 100 g of alumina. The whole is stirred for 24 hours.
• the solid obtained is placed in ambient air for 72 h and then dried in an oven.
• the catalyst is calcined at 500 ° C for 4 hours.
• X-ray diffraction analysis shows the presence of crystalline phase, characteristic of the presence of gamma-alumina.
• a small portion of tetragonal zirconia is detected.
• the specific surface area measured by the BET method is 193 m 2 / g.
• the content of alumina and zirconia measured by X-ray fluorescence is 84.3% and 14.7% by weight, respectively
• Catalyst 2.4 is prepared by coprecipitation of zirconyl nitrate and aluminum sulfate to which ammonia is added. The gel obtained is filtered, dried and then atomized. The powder obtained is shaped by extrusion. The extrudates are then calcined at 700 ° C. for 4 hours. X-ray diffraction analysis results in amorphous zirconia, no streak characteristic of known crystallographic phases of zirconia being detected. The specific surface area measured by the BET method is 158 m 2 / g. The contents of alumina and zirconia are respectively 15% and 85%.
• Catalyst 3.2 is prepared in part according to the teaching of EP-B-0 197 503.
• Catalyst 3.3 is prepared by impregnation of antimony butoxide on Catalyst 1.1. 61.4 ml of antimony butoxide is mixed with 52 ml of heptane and then poured slowly over 82 g of alumina. The whole is stirred for 24 hours. The solid obtained is placed in ambient air for 72 h and then dried in an oven. The catalyst is calcined at 350 ° C for 4 hours. X-ray diffraction analysis shows the presence of crystalline phase, characteristic of the presence of gamma-alumina. The specific surface area measured by the BET method is 155 m 2 / g. The antimony content measured by X-ray fluorescence is 13.8%.
• Catalyst 3.4 is prepared by impregnation of antimony butoxide on Catalyst 1.1. 163.4 ml of antimony butoxide is mixed with 90 ml of hexane and then poured slowly over 150 g of alumina. The whole is stirred for 24 hours. The solid obtained is placed in ambient air for 72 h and then dried in an oven. The catalyst is calcined at 350 ° C for 4 hours. X-ray diffraction analysis shows the presence of crystalline phase, characteristic of the presence of gamma-alumina. The specific surface area measured by the BET method is 128 m 2 / g. The antimony content measured by X-ray fluorescence is 29.3%.
• Catalyst 3.5 is prepared by introducing 86.4 g of alumina gel into a kneader in the presence of 85 ml of an aqueous solution containing 4.5 g of 68% nitric acid. After stirring for 20 minutes, 96 g of Sb 2 O 3 and 20 ml of water are added. After 20 minutes of mixing, the paste obtained is flexible and can be easily extruded. The extrusion is carried out on an extruder equipped with a die of diameter 1.4 mm. The extrudates obtained are dried in a ventilated oven 4 h at 100 ° C and then 3 h at 150 ° C. Then calcination is carried out in a muffle furnace for 3 hours at 350 ° C.
• the specific surface area measured by the BET method is 105 m 2 / g.
• the antimony content measured by X-ray fluorescence is 41%.
• Example 1 (comparative) : Reaction in the absence of catalyst.
• rapeseed oil In a 100 ml autoclave reactor equipped with a stirring system and a temperature and pressure control, 25 g of rapeseed oil are introduced, the composition of which is detailed in the following table and 25 g of methanol.
• Glyceride of fatty acids Nature of the fat chain % by weight Palmitic C16: 0 5 palmitoleic C16: 1 ⁇ 0.5 stearic C18: 0 2 oleic C18: 1 59 linoleic C 18: 2 21 linoleic C18: 3 9 arachidic C20: 0 ⁇ 0.5 gadoleic C20: 1 1 behenic C22: 0 ⁇ 0.5 erucic C22: 1 ⁇ 1
• the medium is heated to 200 ° C. with stirring. The pressure reaches 32 bar.
• Example 1 In a 100 ml autoclave reactor equipped with a stirring system and a temperature and pressure control, 25 g of rapeseed oil are introduced Composition is detailed in Example 1, 25 g of methanol and 5 g of Catalyst 1.3. The medium is heated to 200 ° C with stirring. The pressure reaches 32 bar.
• the concentration of titanium in the methyl ester obtained is less than 1 ppm, this which confirms the heterogeneous nature of catalysis.
• Example 3 is repeated, this time using 5 g of Catalyst 1.6.
• the concentration of titanium in the methyl ester obtained is less than 1 ppm, this which confirms the heterogeneous nature of catalysis.
• Example 3 is repeated, this time using 16.7 g of methanol instead of 25 g. of the Samples are taken after 2 hours, 5 hours and 7 hours. On each sample, after filtration and then evaporation of the excess methanol followed by removal of the glycerol formed by decantation, the concentration of methyl esters is determined by size exclusion chromatography. It is respectively 63%, 78% and 93%
• the concentration of titanium in the methyl ester obtained is less than 2 ppm, which confirms the heterogeneous nature of catalysis.
• Example 3 is repeated, this time operating at 180 ° C. instead of 200 ° C. Pressure reaches 27 bar.
• the concentration of titanium in the methyl ester obtained is less than 1 ppm, this which confirms the heterogeneous nature of catalysis.
• Methanolysis is carried out in an apparatus comprising a fixed-bed reactor, ie a filled column, of diameter equal to 1.9 cm and of length equal to 120 cm, heated by three shells surrounding the column. Preheating of the oil and methanol is done in the column on 10 cm 3 of glass beads and the reaction on 70 cm 3 of volume of Catalyst 1.3. At the outlet of the column was added 20 cm 3 of tungsten carbide and 5 cm 3 of glass beads.
• the inverted U-shaped device consists of a tubular reactor, a cooling on the horizontal part and a decanter, which constitutes the second branch.
• a gas purge system makes it possible to regulate the pressure, that is to say to maintain it initially with nitrogen at the desired pressure of 15 to 60 bar.
• the decanter has at its lower outlet a liquid purge.
• an automatic valve opens to partially empty the product obtained.
• Two pumps inject at selected flow rates and at constant pressure the alcohol and the oil in the column and from bottom to top.
• VVH volume of oil / volume of catalyst / hour
• the product consisting of methanol, glycerol and ester, usually present in a single phase
• the methanol is evaporated off, and the ester is separated and glycerol by settling.
• the ester is analyzed by steric exclusion chromatography. The results are therefore those obtained without any final purification, except that which consists in evaporate the excess methanol and separate the ester from the glycerin by settling, preferably around 50 ° C.
• VVH is the volume of oil injected per volume of catalyst per hour.
• the R ratio is the volume ratio oil / alcohol, denoted H / A.
• Pressure is the pressure that reigns in the decanter, expressed in bar.
• composition of the mixture is expressed in% by weight.
• the concentration of zirconium in the methyl ester obtained is less than 1 ppm, which confirms the heterogeneous nature of catalysis.
• Example 11 is repeated, this time using 16.7 g of methanol instead of 2 g. of the Samples are taken after 2 hours, 5 hours and 7 hours. On each sample, after filtration and then evaporation of the excess methanol followed by removal of the glycerol formed by decantation, the concentration of methyl esters is determined by size exclusion chromatography. It is 53%, 68% and 83% respectively
• the concentration of zirconium in the methyl ester obtained is less than 1 ppm, which confirms the heterogeneous nature of the catalysis.
• Example 11 is repeated, this time operating at 180 ° C. instead of 200 ° C.
• the pressure reaches 27 bar.
• Example 1 In a 100 ml autoclave reactor equipped with a stirring system and a temperature and pressure control, 25 g of rapeseed oil are introduced composition is detailed in Example 1, 25 g of methanol and 5 g of Catalyst 3.3. The medium is heated to 200 ° C with stirring. The pressure reaches 32 bar.
• the concentration of antimony in the methyl ester obtained is less than 2 ppm, which confirms the heterogeneous nature of the catalysis.
• Example 18 is repeated, this time using 5 g of Catalyst 3.5.
• the concentration of antimony in the methyl ester obtained is less than 1 ppm, which confirms the heterogeneous nature of the catalysis.
• Example 18 is repeated, this time using 16.7 g of methanol instead of 25 g.
• the concentration of antimony in the methyl ester obtained is less than 1 ppm, which confirms the heterogeneous nature of the catalysis.
• Example 18 is repeated, this time operating at 180 ° C. instead of 200 ° C.
• the pressure reaches 27 bar.
• the concentration of antimony in the methyl ester obtained is less than 1 ppm, which confirms the heterogeneous nature of the catalysis.

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